Aminotriazine-aldehyde condensation products with linolenic acid monoglyceride and process of making same



Biatented 31, 1948 AMlNOTRIAZINE-ALDEHYDE CONDENSA- TION PRODUCTS WITHLINOLENIC ACID MONOGLYCERIDE AND PROCESS OF MAKING SAME Gustav Widmer,Basel, and Willi Hscli, Binningen, Switzerland, assignors to CiliaProdnets Corporation, Hoboken, N. J.

No Drawing. Application March 8, 1945, Serial No. 581,347

2 Claims. (01. 260-21) This invention is concerned with aldehydecondensation products of triazines of the formula wherein at least oneof the free valencies is substituted by an amine group. It comprises theprocess of manufacture thereof and the new products themselves, as wellas their application in the industry.

This application is a continuation in part of our copending applicationSer. No. 340,199 filed June 12, 1940, now Patent No. 2,387,547, Oct. 23,1945, which is itself a continuation in part of our application Ser. No.68.355 flied March 11, 1936 (now Patent No. 2,310,004). It relates toetherifled aminotriazine-formaldehyde condensation products andparticularly to such etherifled aminotriazine methylol compounds theether groups of which are derived from polyalcohols partially esterifiedwith monobasic organic acids; such ether compounds being articularlyuseful as lacquer and varnish bases.

As typical examples of amino-triazines there may be mentioned the2:4:6-triamino-1z3z5-triazine[CaNs(NH2) a] of the formula considered asderived from melamine by partial desamidation G aNi= (NHr) i GIN]: (NHI) l CgNFNH III N III IV NH V/ H CaNF-"(NHQ CaNg=NH CzNt=NH icf. Journ.Am. Chem. Soc., 44, I, 488 (1922)], or the products wherein one or twoamino groups are substituted by hydroxy, halogen, alkyl, aryl or aralkylgroups, such as for instance 2-hydroxy-4:6-diamino-1:3:5 triazine(ammeline) (Formula VI), 2:4-hydroxy-6-amino-1:3z5-triwhich is commonlycalled melamine, 2:4-difurther melam (Formula III), melem (Formula IV),melon (Formula V) which products may be azine (ammelide) (Formula VII)NHr-C c-on mn-o 0-0:!

I V II v11 N\ /N 'N\ \CI,

NHi OH 2-chloro-4:6-diamino-1:3:5 triazine (Formula 6-methyl-2z4-diamino113:5 triazine (acetoguanamine) (Formula XI). Moreover, also suchamino-triazines may be used wherein the hydrogen atoms of the aminogroup are partially substituted by amino, alkyl, aryl or aralkyl groups,such as 2:4:6-trihydrazino-1:325-triazine (Formula XII) 3 mono-diortrialkyl-melamines, for instance 2 4 G-triethyl-triamino-l :3 -triazine(Formula XIII), mono-dior triaralkylor mono-dior triaryl-melamines, forinstance 2:4:6-triphenyltriamino-1:3:5-triazine (Formula XIV) NEH- 1H:

As is known, the triazines are conceivable also in an isoform of thefollowing formula:

Of course in the case of this isoform also the hydrogen atoms of thecyclic imino groups may be substituted.

As aldehydes there may be used .aliphaticaldehydes, such as for instanceformaldehyde,

'acetaldehyde, crotonic aldehyde, acrolein, further aromatic orheterocyclic aldehydes, such as benzaldehyde, furfurol and the like.

The term aldehydes includes not only the aidehydes themselves, but alsocompounds yielding aldehydes, for instance paraformaldehyde,trioxymethylene, paraldehyde, and the like.

The following description relates, in particular, to the production offormaldehyde condensation products from 2 4 B-triamino- 1 :3 :S-triazine(melamine); however, the description applies with obvious modificationsto other aminotriazines or their derivatives.

Melamine reacts surprisingly freely with neutral aqueous solutions offormaldehyde and in all molecular proportions of melamine toformaldehyde. In the cold, there are formed, by prolonged action, themethylol compounds which at suitable concentration may separate from thesolution in crystalline form. At higher temperatures the methylolcompounds are formed in a shorter time, for example boiling for someminutes and cooling to separate the compound. By the further action ofheat. further condensation occurs with rapid formation of hydrophilicand then hydrophobic resins, the latter separating as a layer oncooling, or even while hot if the reaction is prolonged. By stillfurther heating, there is finally formed a gummy phase, followed byhardening to an insoluble polymerisation product. correspondingly withthe desired condensation product, the reaction may be interrupted at anyphase of the condensation and the product separated in known manner byfiltration, evaporation, precipitation, decantation, drying or the like.In this manner the whole series of the reaction products of the methylolcompounds may find practical application in man directions ashydrophilic and hydrophobic resins.

The hydrogen ion concentration has a very great influence on the speedof the reaction. In the case of neutral or feebly alkalin reaction, thecondensation proceeds in general very gradually. In the case of feeblyacid reaction the speed of condensation isstrongly accelerated; alsostrong alkaline reaction accelerates the condensation.

The desired pH-value may be obtained in known manner by adding inorganicor organic acids or bases or salts thereof.

The condensation may be conducted to produce easily clear, hydrophilicor hydrophobic condensation products with all reasonable molecularratios of melamine to formaldehyde, for example 1:1 up to 1:20. Thehydrophobic properties of the condensation products are liable to beinfiuenced profoundly by the pH-value. The separated hydrophobe resinswhich are not yet polymerized to a very high degree have the outstandingproperty of dissolving to clear solutions in acid. By addition of alkalithey are again precipitated and by further addition of acid pass againinto solution. These properties are not only those of the resinouscondensation products from melamine but are also possessed by themelamine-methylol compounds, and they can be utilized for variouspurposes, for instance for the precipitation of the condensationproducts on fibers.

For the manufacture of commercial condensation products it isfrequentlynot necessary to use so much formaldehyde for the reaction as may be themaximum that can be condensed, since the condensation productsobtainable with a smaller proportion of formaldehyde have also goodcommercial properties.

The condensation may be conducted in several stages by first usingeither melamine or formaldehyde in excess and then causing the mixtureto react in one or more stages with the component which was originallyin deficiency. For example, 1 mol melamine may be caused to react with/2 mol. formaldehyde and the product treated with a further quantity offormaldehyde. However, one may also produce condensation products havingmuch formaldehyde and then bring them into reaction with furtherquantities of melamine.

The reaction between melamine and formaldehyde may occur in an organicmedium instead of in water, in which case there are obtained directlysolutions of the respective condensation products in organic solvents,which are applicable for the manufacture of lacquers or as additions tolacquers, for example nitrocellulose lacquer. Suitable organic solventsare, for instance, ethyl alcohol, butyl alcohol, acetone, glycerine,benzyl alcohol, or the glycerides of the fatty acids of lineseed oil.The condensation ma also be produced in mixtures of water and organicsolvents, for instance in aqueous alcohol of per cent. strength.

Melamine and formaldehyde may also be condensed with exclusion ofsolvent, for example with the use of paraformaldehyde.

The application of solvents is advantageous when the reaction isperformed in a closed vessel (autoclave), when it is possible to selecta reaction temperature above the boiling point of the solvent, forinstance ethyl alcohol.

The formaldehyde condensation products of melamine obtained by thereaction described have very good capacit for being hardened by heat,that is to say they are infusible and insoluble under the influence ofheat. Furthermore, thev prod uct with another natural auaasa are stableto light and free from intrinsic color.

They are, therefore, suitable for very many purposes. for instance asmasses to be cast or pressed in the industry of plastic masses, asbinding; 1 agents forthe production of molded or laminated products;alsov for adhesives, especially in the woodworking industry; in thetextile industry for dressing, anti-creasing, matting and the like, aslacquer binding agents or additions to lacquers.

, In many ofv these applications, particularly-in that of moldedmassesand laminated products, thesurprising stability to heat displayedby the condehsationproducts inthe heat-hardening is ofgreatadvantage,since the operation is not 4 limited to a narrow range of temperaturebut extends. over a considerable temperature interval.

The melamine resins are in this respect similar to the phenol-resins.The formaldehyd condensation products of melamine in their hardenedcondition are surprisingly quite stable to water.

Other aminotriazinesor' their derivatives may be converted into theircorresponding condensation products with formaldehyde in manner'simplied to that outlined above in maybe added to a primarycondensation product made with a suiliclent proportion or an excess of1:3:5-triazlne (I) z-amino-i-hydroxy-fi-phenyl- 1:3:5-triazine (II),Z-methylamino-i-amind-fichloro 1:3:5 triazine (111). 2:4 diam'ino-6-phenylaminc-lzliz5-triazine (IV), Z-amino-izG- diphenylaniino 1:3:5triazine (V) ,i' 2:4:6-trimethylamino-1:3:5-trlazine (VI) ands'o on:

formaldehyde. It also is'possible to mix or condense further theamino-trlazine condensation or artificial resin, forinstancephenol-formaldehyde, or the con-- densation' products from urea orthiourea and formaldehyde. At any stage of thecondensation othersubstances may be added, forinstance dye stuiis, filling materials,plasticizers, water-repelling agents or the like. y g

It has further beenfound that when the reaction-between theaminotriazineand the aldehyde is performed in presence of an organic medium, thislatter may in some cases take part in the reaction. This is'especiallythe case when the condensation is performed in presence of compoundscontaining alcoholic hydroxy groups. These compounds do not only act assolvents, plastiiiants or the like but alsoconstitutively enter into thereaction productforming new compounds the properties of which more orless differ from those of the corresponding compounds made only fromaminotriazine and aldehyde viz. in the absence of compounds containingalcoholic hydroxy groups.

The following description refers especially to these products made fromat least three components viz. an aminotriazine, an aldehyde and acoin-pound containing an alcoholic hydroxy group. The general conditionsof manufacture are an aiog ous to those described above for theproduction of condensation products of aminotriazines with aldehydes.

However, the following may be said especially in respect of thecondensation products made with the concurrence of compounds containingalcoholic hydroxy groups.

The aminotriazines coming into question for this reaction aresubstantially the same as are enumerated above. As further examplesthere may be mentioned: 2-amin-o-4-hydroxy-6-chloro- Also aminoderivatives of other triazines, for instance 1:2: i-triazines may beused, such as for example 3-amino-122:4-phentriazine (VH) 3-amino-1:2:4-phentriazoxin (VIII) of the formula or the like I v Asaminotrl ines there may thus be used generally those derived from theformula )IR 1 t as M.

wherein two A's mean N= and the other two mean densation include monoorpolyhydric alcohols having aliphatic, aromatic, hydroaromatic orheterocycllc radicals. Also compounds which besides the alcoholichydroxy groups contain further reactive substituents, for instancealdehyde-, keto-, carboxyl-, halogenor amino-groups,

which groups may in their turn contain substituents.

Among the individual monoand polyhydric alcohols may be named thefollowing: methyl alcohol, ethyl alcohol, butyl alcohol, ethyl butanol,ethyl hexanoLlauryl alcohol, cetyl alcohol,stearyl alcohol, allylalcohol, oleyl alcohol, glycol, glycerol. erythritol, pentaerythritol,mann'itol, sorb-itol. benzyl alcohol, terpineol, borneol, 'a bietinol,woo1 fat alcohols, furfuryl alcohol or the like.

Among monoand polyhydric alcohols contain ing further substituents theremay benamed ketcand aldehyde alcohols like aldol, glycol aldehyde,glycerol aldehyde; the groups of the carbohydrates, for example glucose,cane sugar, trihexosane or their polymerides, such as dex trine,starches, gufn arable, tragacan'th or the like; hydroxycarboxylic acids,such as tartaric acid, malic acid, ricinoleic acid, saccharic acid ortheir esters or the like; halogen alkyl alcohols, for instancechlorethyl alcohol, glycol chlorhydrin, glycerol chlorhydrin,chloralhydrate; amino-alcohols, for instance mono-, diandtriethanolamine or the like.

Among the polyhydric alcohols those are of importance in which some ofthe hydroxy-groups have been etherified or esterified. As examples ofpartially etherified polyalcohols there may be mentioned glycolmonoethylether, glycerolmonoand diethylether, for instance diethyline, alsocyclohexanone glycerol (-,O"-cyclohexylideneglycerol). As examples ofesterified polyalcohols there may be mentioned the so called esterresins having free hydroxyl groups of the type of the alkyd resins, forexample the esters of glycerolphthalic acid ester, glycerol adipic acidester or glycerol sebasic acid ester which still contain free hydroxylgroups,

of particular value are also those polyalcohols containing at least onefree hydroxyl group the remaining hydroxyl groups being at leastpartially esterified by a monobasic organic acid. As examples ofsuitable monobasic acids there may, besides the lower aliphatic acidssuch as acetic or propionic acid, be particularly mentioned the fattyorganic acids having more than 8 carbon atoms,

such as capric,'lauric, myristic, palmitic, stearic, eleostearic, oleic,ricinoleic acid, further linoleic, linolenic and isolinolenic acid, thelatter three being the foremost known acids of the drying oils, finallythe resin acids such as colophony. As specific examples of suchpartially esterified polyalcohols there may be mentioned the tristearateof pentaerythritoi, the monoor diglycerides of linolenic acid or, moregenerally, of the fatty acids of linseed oil, further the partialglycerides of the fatty acids of China wood oil, oiticica oil, perillaoil, soya bean oil, rape oil, cotton seed oil, cocoa nut oil, fish oil,whale oil, and the like.

When using partially esterified polyalcohols of the type mentioned inthe preceding paragraph, the reaction is advantageously carried out asfollows: The components formaldehyde and aminotriazine or anaminotriazine formaldehyde condensation product particularly one of theinitial condensation stage viz. containing methylol groups, such as forinstance hexamethylolmelamine, are condensed with the partiallyesterified polyalcohol, for instance with a monoor digylceride of amonobasic organic acid, or with a mixture of said monoand diglycerides,in the presence of a low boiling monoalcohol, such as for instancemethyl-, ethylor butyl alcohol.

Instead of the compounds containing alcoholic hydroxy groups themselvescompounds may be used which are converted under the conditions of thereaction into others containing alcoholic hydroxyl groups, for exampleacetals, esters.

Particularly advantageous for the invention are those of the abovementioned groups which are of the type of the carbohydrates and becauseof their easy accessibility in nature.

The bodies which are to react may be brought together simultaneously orin any order of succession. In any case the several component may 8 beadded in stages. Obviously mixtures of the individual components maybeused.

The proportions in which the components re.. act may be varied withinwide limits.

Also other condensation conditions, such as temperature, solvent ordiluent, substances aecelerating the reaction, for instance acids,substances that yield acid, bases or the like are sub- Ject to widevariations.

Water and organic solvents may be used as solvents, also an excess ofthe compound containing alcoholic hydroxy groups and serving as thecondensation component may be used as the solvent.

The reaction may occur in a closed vessel (autoclave) in which case thetemperature of the reaction may be above the boiling point or one orother of the components or the solvent.

The reaction may occur also in absence of a solvent or diluent.

The properties of the new condensation products vary according to theparent material selected as well as the conditions of the reaction. Thusit is possible to produce products which are characterized by lack ofcolor as well as excellent stability to light and heat and of resistanceto chemical action. Their solubility may be varied within wide limits.Products may be obtained which are soluble in water, others which aresoluble in organic solvents and yet others which are insoluble in allthe usual solvents. The products have for the most part a resinousnature and may belong both to the type of resin which i can be hardenedand that which cannot be hard-- ened. In the case of those which arecapable of being hardened this conversion may be eflected by knownmethods, for example by heating or catalytic action. The products whichcannot be hardened may be converted into those which can be hardened by,for instance, the addition of a further proportion of aldehyde,particularly formaldehyde or an agent yielding aldehyde,

In view of the many variations in the properties of the new products,their application are numerous.

The rapidly hardening products either alone or in admixture withplasticising agents or filling agents like fibrous materials yieldmolding powders which can be shaped in a hot press. The molded articlesare of good stability to water andheat and have good mechanicalproperties.

The new products are suitable quite generally as binding agents, forinstance for gluing wood, paper, textile fabrics, for the production ofartificial wood from fibrous material, artificial cork,.

brush cements, for fixing coloring materials, also for the production ofinsecticides and the like .on any kind of support.

The products may also be used for impregnating textile webs and then forbinding these to form homogeneous laminated bodies by means of thehotpress.

A further extensive use for the new materials is in the lacquerindustry. In this connection particularly those products are veryvaluable which are obtained when as the ether group such partiallyesterified polyalcohols are used the ester groups of which are derivedfrom saturated or unsaturated fatty acids (cf. column 12 hereinbefore,last paragraph). The products may be used alone as lacquers. They mayalso be added to lacquers in order thereby to make these harder or morestable to water. They are also important as additions to air dryingoils, for the purpose of making varnishes.

The new products may also be used for making shaped bodies by a castingprocess; in this case there may be obtained bodies clear as glass andresistant to water as well as of good mechanical strength. I

In textile chemistry the new substances find a Wide application, forinstance as finishes. as noncreasing agents, for diminishing a capacityfor swelling, as thickening or stifiening agents or as softening agents,as agents for making fillers or finishes fast to water, in thepreparation of dyed or printed material.

- Theproperties of the products may be further modified if the reactioncomponents viz. aminotriazines, bodies containing alcoholic hydroxygroups and aldehydes are used with the simultaneous or subsequentaddition of further bodies which are capable of reacting with anaminogroup, an alcoholic hydroxy group or an aldehyde group. As suchadditions may be named, for example, amines, amides, for instanceaniline, urea, thiourea, sulfamide, phenols, acid chlorides or the like.Such an addition is advantageous, for example, when one of the threeprimary components is used in excess. of various condensation productsare produced.

When aminotriazines,. v aldehydes and compounds containing alcoholichydroxy groups are used which contain besides their amino group orgroups, alcoholic hydroxy group or groups and/or aldehyde group orgroups respectively still further reactive groups, for instance halogen,carboxyl, carbonyl, hydroxyl or amino groups, it is possible tocausethese groups to enter wholly or in part into reaction with furtherreactive bodies such as acid chlorides or anhydrides, alcoholates, saltsof carboxylic acids, amines or amides. For this reaction substances arealso applicable which are on their own account capable of entering intoreaction simultaneously or subsequently with further reactive bodies.

It is also possible to mix the new condensation products with artificialor natural resins or to condense them therewith. Also at any stage ofthe condensation further substances, for instance dyestufis, fillers,softeners, dehydrating agents or water-proofing agents may be added.

. The following examples illustrate the invention, the parts being byweight unless otherwise stated and the parts by volume and the parts byweight bearing the relationship to one another as that of the litre tothe kilo:

Example 1 A mixture of 12.6

parts (0.1 mol.) of melamine of the formula In this case mixtures Itsanalysis indicates the formula:

CaHsNaBCI-IaQI-IaO calculated as. 2 6.2 25.9 obtained 33.2 6. 2 26.5

Example 2 126 parts of melamine (1 mol.), 360 parts by volume ofalcoholic formaldehyde solution of 41.8 per cent. strength (5 mol.), 300parts by volume of alcohol and 1 part by volume of concentratedhydrochloric acid (0.01 mol.) are heated together under reflux toboiling. After about 15 minutes the whole is dissolved. After 45minutes, the clear solution is cooled. If a sample thereof is dilutedwith water a resin separates immediately. A sample poured upon glass andhardened at 150 C. yields a hard, clear film.

Example 3 50 parts of a methylol-compound of melamine, obtained asdescribed in Example 1, are added to parts by volume of butyl alcoholand 0.5 part by volume of concentrated hydrochloric acid and the mixtureis heated to boiling for hour. A quite clear solution is obtained whichdries and hardens quickly to a hard varnish when heated to a thin layer.Such solutions in butyl alcohol may be added, for example, tonitrocellulose lacquersin order to lend them hardness and fillingcapacity.

Example 4 126 parts of melamine (1 mol.) are condensed with 280 part-sby volume of neutral formaldehyde solution of 32 per cent. strength byvolume -(3 mol.) in a reflux apparatus on an open flame by boiling for30 minutes and the solution obtained is evaporated in a vacuum at about60 C. to produce a thick syrup. The latter. preferably after addition ofa softening agent, for example glycerine, is poured into molds andhardened by gradually increasing the temperature.

The cast masses have an appearance as bright as water and clear ascrystal and are of good hardness and stability to water.

Example 5 50 parts of nitrocellulose /z-second-wool") are dissolved in amixture of 10 parts of tricresylphosphate, 10 parts of butyl alcohol, 50parts of ethylacetate and 40 parts of toluene. Into this very thickpasty solution there are stirred parts of an alcoholic solution ofmelamine resin (see Example 2). The solution thus obtained is as clearas water and is diluted for use with a mixture of equal parts oftoluene, absolute alcohol and ethylacetate. The solution is cast onglass or metal and dried, and yields a layer which is as clear as waterand as smooth as a mirror and amaeae l l hardens when the temperature isgradually increased, and whenfinallya temperature of 120 C. has beenapplied for half-an-hour yields films of very good stability to waterand of good hardhess.

Example 70.8 parts (0.2 mol.) of symmetrical triphenylmelamine of theformula manila-( 1 o-rmcuh o fi HCH are dissolved in a reflux apparatuson the boiling watehbath together with 63.5 parts by volume of alcoholicneutral formaldehyde of 42.6 per cent. strength by volume (0.9 mol.01120), 0.6 part by volume of concentrated sulfuric acid and 63.5 partsby volume of alcohol of 95 per cent. strength. After some minutes aclear solution is produced which after being cooled in ice-water becomuopalescent. The condensation product thus formed is neutralized withalcohol caustic soda and then completely precipitated by addition ofice-water. It is separated from water by filtration and is dried at 60C. in'a drying chest. There is produced a white powder which when meltedat 150-200 C. becomes a brittle, clear resin, insoluble in alcohol andbenzine but soluble in benzene, toluene, acetone or the like.

Example 7 A mixture of 7.3 parts of finely pulverized 2-chloro-4.6-diamino-1.3.5-triazine (mono-chloromelamine) of the formula(/20 mol.), 22 parts by volume of formaldehyde of 40.8 per cent.strength by volume (V20 mol.), 12 parts by volume of alcohol of 95 percent. strength and 1 part by volume of sulfuric acid of 50 per cent.strength by volume is heated to boiling in the water bath while shaking,whereby everything is dissolved in the course of a few minutes. Thesolution then becomes turbid and it is therefore further boiled in areflux apparatus on the open flame for about /2 hour until a clearsolution is produced. The latter is evaporated in avacuum, whereby acondensation product, in the form of a syrup clear as crystal, isobtained. By diluting with water, alcohol or alkali solution the productis precipitated in the form of white amorphous precipitate.

If, for example, the white precipitate obtained from 10 parts of thissyrup by neutralizing it with NaOH is ground finely with 15 parts byvolume of alcohol there is obtained a suspension which can be coated. Ifthis is applied as a thin layer on veneer wood laid cross-wise and gluedfor halfan-hour at 100 C. under a pressure of 5-10 kilos per sq. cm. anormal veneer plate of good resistance to water is obtained.

If, for example, 15 parts of the acid chloromelamine-resin in the formof syrup are mixed with "1 parts of wood-meal, the mixture dried at 80C. and ground together with 0.6 part of calcium carbonate there isobtained a molding pow- 2 der which, when molded at 150-180 C. under apressure of about 300 kilos per sq. cm. yields mechanically very strong.bright brown, trans parent products of good stability to water.

Example 8 6.3 parts of melamine /zo mol.), 15 parts by volume ofalcoholic formaldehyde of 41.8 per cent. strength by volume (about /20mol.), 15 parts by volume of absolute alcohol, 0.1 part by volume ofconcentrated hydrochloric acid /ioo mol.) and 6 parts of themono-glyceride of linolenic acid are caused to react with each other for3 /2 hours under refiux on the boiling waterbath. There is produced asomewhat turbid, feebly yellowish, oily liquid. which, on furtherevaporation finally solidifies to a tough, clear, gummy mass. If,however, the oily condensation product before solidification is dilutedwith some benzene. preferably after addition of siccative, and appliedon a support and dried in the air. there is obtained after some time aclear, transparent, hard coating which can no longer be scratched by thefinger nail.

of formic acid and 8.5 parts by volume of an alcoholic solution offormaldehyde of 42.8 per cent. strength by volume ("/wo mol.) and 1 partby volume of sulfuric acid of 50 per cent. strength are added and thewhole is heated in the oil bath at C., whereby the alcohol is in greaterpart evaporated. After about 30 minutes an almost completely clearsolution of the condensation product is formed. which rapidly becomesoily and finally gelatinous.

If the condensation solution before it gelatinizes is poured on glassand kept in an oven at 60 C. it first gelatinizes and then hardens to ahard, clear film.

If the condensation solution is mixed with alcohol, water, a solution ofbase or the like, a white, amorphous product is precipitated.

If the condensation solution is diluted however. for example with hotformic acid, there is obtained a solution which, according to the degreeof dilution, may be completely diluted with water or, when diluted withwater, yield opalescent to whitish colloidal solutions from which bysalting out or neutralization the amorphous condensation product ofmelam is precipitated.

Example 10 A mixture of 126 parts of melamine (1 mol.), 214 parts of analcoholic solution of formaldehyde of 42 per cent. strength (3 mol.),200 parts of absolute alcohol and 1 part of concentrated hydrochloricacid (about 0.01 mol.) is heated to boiling for 1 hour. The solutionthus produced is neutralized with 1.3 parts of caustic soda solution of30 per cent. strength, filtered, if desired, and kept at the boil for 3hours; it is then cooled. There is produced a clear condensationsolution which leaves a clear varnish when dried. The solution may beused alone as a varnish or in conjunction with other substances having aplasticising effect or formin varnishes which are known in the lacquerindustry.

If a sample is evaporated to a constant weight Example 11 A mixture of126 parts of melamine (1 mol.) and 300 parts of neutral formaldehydesolution of 30 per cent. strength (3 mol.) is heated on the boiling.water bath until a sample diluted with water yields a precipitate of.resin. The solution is then evaporated to dryness in a vacuum andfurther treated at 100 C. for 1 hour in a vacuum.

5 parts of this product are treated at 130 C. with 8 parts-of purebenzyl alcohol. A clear solution is obtained in a short time; a sampleof it, however, gives a further precipitate on cooling. After a fewminutes a sample remains clear on cooling but on addition of benzylalcohol gives a precipitate. water and formaldehyde. After hour theviscosity has risen considerably. A sample when mixed'cold with anydesired proportion of benzyl alcohol or with a limited proportion ofbenzene remains clear. The whole is dried in a vacuum of about 0.07 mm.of mercury at 100 C. until the weight. is constant, whereby there isobtained a. product which is. glass-clear and of foamy structure: itsweight is now about 28 per -cent. hijg'her than that of the quantity ofmelamine formalde- -hyde condensation product used.

By further condensation at 130 C. the condensatezafter about hourbecomes highly viscous and has a tendency to gelatinize. A sample ofthis product dried at 100 C. in a vacuum under a pressure up to 0.04 mm.of mercury until the weight is constant and finally in the form ofpowder shows an increase of weight of 38 .per cent.

For 1 mol melamine, therefore, approximately "4 mol .benzyl alcohol habeen condensed in the new product.

Example 12 126 parts of melamine (1 mol.) are dissolved in 650 parts ofa neutral solution of formaldehyde of 30. per cent. strength (6.5 mol.)heated to 90 C.; the solution is kept at 90 C. for 5 minutes andthencooled. When the temperature has fallen to 60 C. 600 parts ofalcohol are added and the cooling is continued. The white mass which hasseparated is filtered, washed with aqueous alcohol of '50 per cent.strength and dried. The product consists in greater part ofhexamethylolamine CaNs(CH2OH) s.H2O.

100 parts of this product are dissolved in 200. partsby volume ofmethanol under addition of fi parts by volume of a all solution ofhydrochloric acid in" methanol at boiling temperature. The solution iskept boiling for some hours and then evaporated in vacuo. A clear resinis obtained which may be used for instance as a lacquer or lacquersubstitute.

From the determination of the methoxy content according to'the method ofZeisel it results that the resin has chemically bound 3 moles ofmethanol for each moi of melamine.

Example 13 324, parts of the hexamethylol melamine made according toExample 12, paragraph 1 (1 mol.)

The solution continues to evolve 14 are treated on theboiling water bathwhilst stir.- ring with a solution of parts of hydrochloric acid (0.1mol.), 200 parts of ethyl alcohol and 1400 parts of ethyl-2-hexanol.After 20 minutes .a slightly turbid solution is produced. Afterrl hour,the wholeis cooled. The product consists of two layers; 500 parts of itare distilled in a vacuum on the boiling water bath whereby .ahomogeneous solution is produced. This is illtered if necessary and thenevaporated in a vacuum to a thick syrup. This syrup is soluble inbenzene and 'benzine and any other solvents.

Example 14 120 parts of para-formaldehyde (4 mol.) are dissolved in1200. parts of allyl alcohol with the aid of heat and 126 parts ofmelamine (1 mol.) are added; The mixture is heated to boiling. In a fewminutes a clear solution is produced and this is maintained for 4 hoursat the boil and then evaporated at-100 C. first in a vacuum of 10 mm.and then. in avacuum of about 0.1 mm. until all odour has disappeared.There is obtained a fusible resin which is viscous at 100 C. andsolidifies when cold.- At-'. l50 C. it gradually hardens.

Example 126 parts of finely ground melamine (1 mol.), 1150 parts of analcoholic solution of formaldehyde of '40 per-cent. strength (6 mol.)and 1 part of concentrated hydrochloric acid (0.01 mol.) are togetherheated in the boiling water bath for 10-15 minutes until all isdissolved. There are then added 100 parts of cetyl alcohol and the wholeis treated in the boiling water bath for l to 1 /2 hours and thencooled. Instead of cetyl alcohol. lauryl alcohol, stearyl alcohol, oleyialcohol, terpineol, alcohols of wool fat, castor oil, tartaric aciddiethyl ester, diethyline (glyceroldiethyl ether),glycerolmonochlorhydrin, cyclohexanonglycerol (0.0" cyclohexylideneglycerol) or the likemay be used. In all cases a clear solution isproduced which on cooling either remains clear or becomes a whiteviscous liquid or paste. Independently of this appearance all theproducts are glass-clear when they are dissolved in acetone or when thevolatile solvent has been evaporated.

Example 16 126.,parts of melamine v(1 mol.) arecondensed with v300 partsof neutral formaldehyde solution of 30,per cent. strength (3 mol.) untila cooled sample of the clear solution yields a precipitate of. resinwhen diluted with water. glycerol are now added and the mixturedistilled in the boiling water bath in a vacuum of 12 mm. The internaltemperature gradually rises to 92 C. The distillation of water has thenpractically ceased, but the product is still treated for 2 hours in avacuum of about 12 mm. and then for 1 hour in a vacuum of about 3-4 mm.in the boiling water bath. The clear mass is cast into a mould andhardened for hours at 110 C. There is produced a clear, very hard andmechanically good casting.

Instead of glycerol another for instance glycol.

Example 17 126 parts of melamine (1 mol.) are dissolved in the boilingwater bath in 200 parts of neutralized formaldehyde solution of percent. strength (2 mol.) and are kept in the water bath until a cooledsample yields a precipitate of resin immediately on mixing with an equalquantity alcohol may be used,

parts of of water. '70 parts of water are then distilled in a vacuum andthe mass mixed with 55 parts of glycerol, 110 parts of wood flour and acolouring matter and then kneaded on hot rollers until a skin isproduced. The latter is comminuted. The product thus obtained may bemoulded in a hot press, for example at 145 C., for 3 minutes to producea good hard molding which after 24 hours immersion in cold waterincreases 1 per cent. in weight and after 10 minutes immersion inboiling water increases 1.5 per cent. in weight.

Example 18 126 parts of finely ground melamine (1 mol.), 450 parts of-analcoholic solution of formaldehyde of 40 per cent. strength (6 mol.) andalcoholic hydrochloric acid (0.01 mol.) are treated together in theboiling water bath until all has dissolved. The solution is now mixedwith 0.01 mol. of alcoholic caustic soda (solution A).

(a) The solution A is mixed with 372 parts of ricinoleic acidmono-glyceride (1 mol.) and 200 parts of absolute alcohol. There isproduced a clear solution which is kept for hours at the boil. Theproduct thus obtained is poured on to a support and dried in the oven;there is produced a clear soft film.

(b) 148 parts of phthalic anhydride (1 mol.) and 92 parts of glycerol (1mol.) are kept together at 160 C. for 22 hours. There is produced aresin having an acid number of 70. This resin is mixed with the solutionA, 200 parts of benzene and'200 parts of absolute alcohol and the wholeis kept at the boil for 5 hours. There is produced a. clear solutionwhich may be used as a varnish.

(c) 92 parts of glycerol (1 mol.), 148 parts of phthalic anhydride and200 parts of absolute alcohol are dissolved in solution A and thesolution thus obtained is treated in the form of a thin layer in theoven. There is obtained in this manner a very hard lacquer.

Example 19 146 parts of adipic acid (1 mol.) and 101.2 parts of glycerol(1.1 mol.) are heated together first for 1 hour at 155-160 C. and thenwithin 1 hours gradually to 230 C. until the limit of gelatinization hasbeen attained and the acid number is 30.7 whereupon the whole isimmediately cooled and dissolved in a mixture of 100 parts each ofabsolute alcohol and benzene.

63 parts of melamine (0.5 mol.) are boiled together with 225 parts ofalcoholic formaldehyde solution of 40 per cent. strength (3 mol.) untilan almost clear solution is produced.

These two solutions are mixed and the mixture is boiled for 12 hours.The solution thus obtained dries on a support to dazzling clear lacquer.

Example 20 126 parts of melamine (1 mol.), 126 parts of mannitol and 500parts of commercial formaldehyde solution of 36 per cent. strength (6mol.) are condensed together for 1 hours at 70 C. and then evaporated ina vacuum to dryness. The product thus obtained is moulded for 6 minutesin the hot press at 150 C. whereby transparent mouldings are producedwhich, when immersed in cold water for 24 hours increase in weight by 1per cent. and when treated for 10 minutes in boiling water increase inweight by 1.8 per cent.

Example 21 126 parts of melamine (1 mol.), 126 parts of cane sugar and600 parts of neutral formaldehyde solution of 30 percent. strength (6mol) are heated together in the boiling water bath until a sample of theclear solution diluted with water yields a true separation of resin. Thecondensation solution is then dried in a vacuum to a product of foamystructure which is comminuted and after-treated at C. until a fluidityfavourable for moulding in the hot press has been obtained. If thisproduct is moulded for 6 minutes at C. there is produced a hardglass-clear moulding which when stored in water for 24 hours increasesin weight by 0.1 per cent. and when boiled in water for 10 minutesincreases in weight by 2.3 per cent.

11', instead of sugar, trihexosane (compare Helv. Chim. Acta, vol. 5,page 642, 1922) or soluble starch is used and the procedure is analogousthere is obtained a moulding which is also glass-clear; this increasesin weight after immersion for 24 hours in water 0.4 per cent. or 0.5 percent. and when treated for 10 minutes in boiling water 0.6 per cent. or2.6 per cent. By subsequently storing the mouldingthus treated withwater the new weight changes a little. The weight, however, is neverbelow the original weight.

Example 22 126 parts of melamine (1 mol.), 126 parts of trihexosane and600 parts of neutral formaldehyde solution of 30 per cent. strength (6mol.) are treated for 40 minutes in the boiling water bath. Thecondensation product thus obtained is then brought to dryness in avacuum. The dry product is soluble to a clear solution in a limitedquantity of cold water.

100 parts are mixed with 6 parts of ammonium sulfate and the mixture isdissolved in 50 parts of water. Canadian birch veneers of 2 mm.thickness are painted with the solution and laminated in the usualmanner to a three-ply wood which is then pressed for 12 minutes under apressure of at least 4 kilos per sq. c., at 100 C. The glueing is stableto boiling water and of high strength.

Example 23 252 parts of melamine (2 mol.), 400 parts of commercialformaldehyde of 30 per cent. strength 4 mol.) and 3'70 parts of canesugar are heated together on the water bath for A hour. When a sampleyields a precipitate of resin on dilution with water a condensationsolution is kneaded with 270 parts of cellulose and the mixture is driedand ground. The powder thus obtained is moulded, for example for 2minutes at C. whereby mouldings are produced which, when stored in coldwater increase in weight by 4 per cent. and when treated for 10 minutesin boiling water increase in weight by 2.2 per cent.

Example 24 17 diluted with water to form a feebly opaiescent solution.The addition of alkali lye produces a precipitation.

This product may be used, for example, as a thickening agent in variousbranches of industry, for example in textile chemistry.

Example 25 126 parts of melamine (1 mol.), and 131 parts ofparaformaldehyde (4.4 mol.) are dissolved together in 1250 parts offused choralhydrate and the solution is kept at the boil for about 2hours until it has become viscous. The product is now treated in avacuum of about 10 mm. in the boil-' Example 265* 126 parts of finelypulverlsed melamine (1 mol.), 450 parts of alcoholic formaldehydesolution of 40 per cent. strength, mol.) and 0.01 mol. of alcoholichydrochloric acid are together heated in the boiling water bath untilall has dissolved. 120 parts of urea (2 mol.) are now added and the massfurther treated in the boiling water bath for about /z hour. Thesolution thus obtained is viscous when cold. It may be diluted withalcohol and may be used as avarnish.

Example 27 126 parts of melamine (1 mol.), 130 parts oipara-formaldehyde (6 mol.) and 660 parts of glycerol chlorhydrin aretogether kept at 90 C. for 3 hours. The clear solution is then mixedwith 3000 parts of water and thoroughly stirred. There separates a resinof silky lustre. The mixture is then cooled with ice while kneading. Inthis manner the resin acquires a tough consistency. The supernatant,nearly clear water is poured 0d and the resin is kneaded with 500 partsof water for the purpose of further washing it. The resin separated fromthe washing water is now dried in a vacuum at a moderate temperature andthen dissolved in 900 parts of glycol-monomethyl ether. The clearsolution A thus obtained contains about 30 per cent. of resin and theresin itself contains about 11 per cent. of chlorine. There is thereforemore than 1 mol. of glycerol chlorhydrin present in the resin per mol.of melamine.

1300 parts of solution A (containing about 1 mol. of melamine) and 320parts of dry potassium linoleate (1 mol.) dissolved in 320 parts ofglycol monomethyl ether are mixed together and the mixture is heated toboiling. After 2 /2 hours, as will be apparent from the quantity ofpotassium chloride which has separated, the larger part of the potassiumsoap has been decomposed. The mixture is kept at the boil for 9 hours.After this time the reaction is practically complete. The clear solutionthus obtained is separated from the deposited potassium chloride and maybe used as a varnish.

Example 28 202 parts of 2:4-diamino-6-phenylamino-1:3 triazine (1 mol.)and 318 parts of benzaldehyde formaldehyde (3 (3 mol.) are dissolved in250 parts of boiling butanol and the solution is kept at 100 C. for Vhour. There is produced a solution which remains clear in the cold andsolidifies in the oven to a hard clear varnish.

Example 29 278 parts of 2-amino-4:G-diphenylamlno-l 23:5- triazine (1.mol.), 300 parts of an alcoholic solution of formaldehyde of 40 percent. strength (4 mol.) and 300 parts of absolute alcohol are kept atthe boil for 1-2* hours. There is produced a clear solution which, whendried, leaves a clear varnish.

Exam le 30 200 parts of 2-amino-4-hydroxy-6-phenyl- 1:3:5-triazine (1mol.) and 90 parts of paramol.) are mixed with 600 parts of glycol. Themixture is first kept at the boil for about 10 minutes until a clearsolution is produced; the latter is then treated for hour at 150 C.There is produced a solution which remains clear in the cold.

Example 31 163 parts of 3-amino-1z2z4-phentriazoxine (1=' mol.), 300parts of formaldehyde solution of 30 per cent. strength (3 mol.), 100parts of n-hydrochloric acid (0.1 mol.) and 1000 parts of water aretogether heated in the water bath. After few minutes resinous clumpsform in the mixture. The whole is treated while kneading for anotherhour in the water bath and then cooled. The solidified resin iscomminuted, filtered, washed and dried.

1 part of this resin is dissolved together with 0.6 part of glycol in 50parts of ethyl-2-butano1 with aid of heat. On cooling the resinprecipitates again. The mixture is now kept at the boil for 8 hours.After this treatment precipitation does not take place on cooling. Thesolution is clear and on evaporation leaves a resin which is hard andclear when cold.

Example 32 off on the descending cooler, while constantly replacing thebutanol distilled over. The resin solution is filtered, if necessary,and then evaporated in vacuo at a temperature below 100 C.

The tough v- ;cous resin thus resulting dissolves in benzenehydrocarbons or mixtures thereof with lacquer benzine or butanol. Thesolutions when sprayed on surfaces cure at C. within 30-450 minutes toform elastic, hard and water resistant coats.

Example 33 200 .parts of wood oil are heated in a. stream of nitrogenfor 1 hours up to 245 C. with 400 parts of purified linseed oil, 82parts of pure glycerine and 0.7 part of caustic soda. 30 parts of themixed glyceride thus obtained containing free hydroxyl groups aredissolved in '10 parts of ethanol together with 20 parts of a linseedoil glyceride obtained according to Example 32, whereupon 22 parts ofbexamethylolmelamine and 1.5 parts of phthalic Example 34 460 parts oflinseed stand oil (cf. Ellis Chemistry of Synthetic Resins, 1935, pages199 and 1216) are heated in the nitrogen stream for 1 hour to 250 C.with 65 parts of pure glycerine and 1 part of caustic soda solution of40 per cent. strength. 47 parts of the product thus obtainedrepresenting a mixture consistin mainly of monoand diglycerides oflinolenic acid are dissolved in 6'7 parts of 'butanol, whereupon partsof technical lactic acid and 43 parts of hexamethylolmelamine are addedand the mixture is heated. while stirring, in an oil bath at thedescending cooler at an external temperature of 130 C. A mixture ofbutanol and water distils off, care being taken that the but'anoldistilled off is constantly replaced. After about 5 hours the mixture isevaporated in vacuo, diluted with toluene and filtered. A lacquer isobtained which when stoved at 150 C. yields clear, elastic and water Iresistant films.

Example 35 300 parts of colophony and 300 parts of linseed oil areheated in a nitrogen stream for 1 hour to 250 C. with 150 parts of pureglycerine and 0.9 part of caustic soda. At the end of the reaction theglycerine in excess is eliminated by intensifying the nitrogen stream.47 parts of the resulting mixture of monoand in 70 parts of butanol,whereupon 32 parts of hexamethylolmelamine and 1.5 parts of phthalicanhydride are added. The mixture is then heated while stirring in an oilbath for about 5 hours at an external temperature of 130 C. so that amixture of butanol and water slowly distils off, the butanol beingconstantly replaced. Then the mixture is evaporated in vacuo and asolution in a. suitable solvent is made. A lacquer is obtained whichalready at 105 C. yields hard clear coats.

When the curing temperature is 150 0.; extraordinary short bakingtemperatures are needed. The coats are highly water resistant.

Example 36 30 parts of a mixed colophony linseed oil glyceride as usedin Example 35 are dissolved in 70 parts of butanol together with 20par-ts ofcastor oil and 1.5 parts of phthalic anhydride, whereupon 32parts of hexamethylolmelamine are added. The working up of the mixtureis the same as described in the foregoing example. The resultinglacquer, when heated to 150 0., yields in a very diglycerides aredissolved 20 short time clear. hard and smooth coats of good elasticityand extraordinary resistance even towards boiling water. Hardening maybe effected already at C. within 1 or 2 hours.

Insteadof an alcoholic solution of a methylolmelamine an ether of'methylolm'elamine with -a low boiling monoalcohol may be used forcondensaltion with the partially'esterified polyalcohol.

What we claim is:'

:1. A process for the manufacture of condensationproduct's'characterized by causing to react, in presence of a lowboiling monoalcohol, a formaldehyde condensation product of anaminotriazine of the formula i wherein at least one of the freevalencies of the wherein at least one of the free valencies of thenucleus is substituted by an amino group having at least one reactivehydrogen atom, the remaining free valencies being taken up by a radicalselected from the group consisting of hydrogen, hydroxyl halogen, aikyl,alkylene, aryl and aralkyl, with the monoglyceride of linolenic acid,said linolenic acid being the sole acid constituent ofthe saidmonoglyceride.

GUSTAV WlDMER. WILLI FISCH.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,294,590 West Sept. 1, 1942FOREIGN PATENTS Number Country I Date 867,109 France June 30, 1941Certificate of Correction Patent No. 2,448,338. August 31, 1948.

GUSTAV ET- AL.

It is hereby certified that error appears'in the printed specificationof the above numbered patent requiring correction as follows: Column 8,lines 69 and 70, for column 12 hereinbefore, last paragraph read column7 hereinbqfore, second paragraph; and that the said Letters Patentshould be read with this'correction therem that the same may conform tothe record of the case in the Patent Office.

Signed and sealed this 30th day of November, A. D. 1948.

THOMAS E MURPHY, V

' Assistant flonnniaeioner of Patents.

